Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2282—Unsaturated compounds used as ligands
  • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/48—Zirconium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
  • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
  • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
  • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• This invention relates to a new supported catalyst system capable of producing polyolefins having a broad or narrow molecular weight distribution, and in particular to a titanium catalyst supported on a functionalised carrier which optionally has impregnated therein a polymerisation active metal complex, e.g. a metallocene.
• a polymerisation active metal complex e.g. a metallocene
• titanium and metallocene catalysts for the polymerisation of olefins is well established in the art. Numerous documents describe the use of titanium catalysts either alone, or more conventionally supported on a carrier, e.g. an oxide support such as silica or alumina. Such supported catalyst systems are used either without a cocatalyst or with a metal alkyl cocatalyst as is well known in the art. Titanium catalysts are also widely employed in Zielger systems often in combination with magnesium chloride.
• Metallocene catalysts are also widely employed and are conventionally used in combination with a cocatalyst as is well known in the art.
• Bimodal or multimodal polyolefins may be prepared by melt blending; however to ensure satisfactory homogeneity it is preferred to use a multi-stage polymerization process, e.g. using two or more reactors in series, to produce bimodal or multimodal polyolefins .
• Bimodal or multimodal polyolefins are advantageous in that they may combine the good mechanical properties associated with a high molecular weight component with the processability associated with a low molecular weight component. It would be useful if a catalyst system were available which comprised two sites, one of which was sensitive to hydrogen concentration, the other of which was essentially unaffected by the amount of hydrogen present.
• the polymer support used in the present invention may for example be a functionalised polystyrene as described in US-A-4, 623 , 707.
• This Patent teaches the use of a functionalised polystyrene carrier in supporting a Ziegler-Natta catalyst and is herein incorporated by reference.
• the functionalised supports have previously been described, never before have they been proposed for use with a titanium catalyst precursor and optionally a polymerisation active metal complex, allowing the formation of polyolefins having highly controllable molecular weight distributions.
• the invention provides a supported titanium catalyst system comprising a titanium catalyst bound via at least one heteroatom, e.g. a nitrogen, sulphur or oxygen atom, to a functionalised support, said heteroatom being connected to said support via an organic group.
• a polymerisation active metal complex e.g. a metallocene.
• the invention provides a process for the preparation of a supported catalyst system comprising:
• the invention provides the use of a supported catalyst system as hereinbefore described in the polymerisation of olefins .
• the invention provides a method of polymerisation comprising polymerising at least one olefin in the presence of a supported catalyst system as hereinbefore described.
• the invention provides polyolefins prepared using the supported catalyst system as hereinbefore described.
• the titanium catalyst precursor may be selected from a wide variety of suitable precursors readily determined by the person skilled in the art.
• the titanium ion should preferably be in the 3+ or 4+ oxidation state.
• the titanium catalyst precursor should carry at least one, e.g. two groups which are capable of being displaced by the heteroatoms present on the support .
• Suitable leaving groups will be readily determined by the artisan.
• suitable titanium catalyst precursors include those of formula (I)
• each A independently represents any group or groups which remain bound to the titanium after contact with the support or a leaving group which may be displaced by reaction with the support; and x is an integer of 3 or 4.
• Suitable groups A therefore include an ⁇ -ligand, for example an open chain ⁇ 3 , ⁇ 4 or ⁇ 5 ligand or a closed ring ⁇ 5 ligand such as cyclopentadienyl, indenyl, or fluorenyl ligand, halogen (e.g. chlorine, bromine or iodine, especially chlorine), alkenyl (e.g. allyl or substituted allyl, e.g.
• At least one group A must of course be capable of being displaced by an active group on the support surface .
• leaving group is meant a group which is capable of being displaced by a heteroatom attached via an organic group to the support .
• A represents a closed ring ⁇ 5 ligand, this may be, for example, of formula II
• Cp is an unsubstituted, mono-substituted or polysubstituted homo or heterocyclic cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, benzindenyl, cyclopenta [1] phenanthrenyl, azulenyl, or octahydrofluorenyl ligand or a heterocyclic analog thereof, e.g.
• each Y which may be the same or different is a substituent attached to a ring atom of Cp and selected from halogen atoms, and alkyl, alkenyl, aryl , aralkyl , alkoxy, alkylthio, alkylamino, (alkyl) 2 P, siloxy (e.g. alkylsiloxy) , germyloxy (e.g.
• alkylgermyloxy) , acyl and acyloxy groups or one Y comprises an atom or group providing an atom chain comprising 1 to 4 atoms selected from C, 0, S, N, Si, Ge and P, especially C and Si (e.g. an ethylene group) to a second ⁇ -ligand of formula II, e.g. an unsubstituted, mono-substituted or polysubstituted homo or heterocyclic cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl ligand group.
• a second ⁇ -ligand of formula II e.g. an unsubstituted, mono-substituted or polysubstituted homo or heterocyclic cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl
• any hydrocarbyl moiety preferably contains up to 20 carbon atoms, more preferably up to 10 carbons, especially up to 6 carbons.
• the rings fused to the homo or hetero cyclopentadienyl rings may themselves be optionally substituted e.g. by halogen atoms or hydrocarbyl groups containing 1 to 20 carbon atoms.
• Suitable ⁇ -bonding ligands include the following: cyclopentadienyl, indenyl, fluorenyl, pentamethyl- cyclopentadienyl, methyl-cyclopentadienyl, 1, 3 -dimethyl-cyclopentadienyl , i-propyl-cyclopentadienyl, 1,3- di-i-propyl-cyclopentadienyl , n-butyl-cyclopentadienyl , 1, 3-di-n-butyl -cyclopentadienyl, t-butyl- cyclopentadienyl, 1, 3-di-t-butyl-cyclopentadienyl , trimethylsilyl -cyclopentadienyl , 1, 3 -di-trimethylsilyl- cyclopentadienyl, benzyl-cyclopentadienyl, 1,3-di-
• titanium species binds to more than one heteroatom present on the support
• one titanium: support heteroatom bond to be formed in a vacant titanium coordination site whilst the other titanium: support heteroatom bond is formed via displacement of a leaving group present in the catalyst precursor.
• the bonds between the heteroatoms present on the catalyst support and the titanium catalyst precursor preferably form directly from the titanium ion, i.e. a titanium ion to heteroatom bond.
• the titanium ion may be in any convenient oxidation state, e.g. 0, 3 or especially 4.
• titanium catalyst precursors are titanium halides, titanium alkoxides, titanium amides, titanium alkyls, and combinations thereof.
• the titanium catalyst precursor is a titanium tetrahalide, especially titanium tetrachloride .
• the support may be impregnated with a polymerisation active metal complex, e.g. a metallocene.
• Suitable metallocene catalysts for use in the invention may be any conventional metallocene catalyst .
• the term metallocene is used to refer to all catalytically active metal : -ligand complexes in which a metal is complexed by one, two or more open chain or closed ring ⁇ -ligands.
• bridged bis- ⁇ -ligand metallocenes, single ⁇ -ligand "half metallocenes" , and bridged ⁇ - ⁇ ligand "scorpionate” metallocenes is particularly preferred.
• the metal in such complexes is preferably a group 4, 5, 6, 7 or 8 metal or a lanthanide or actinide, especially a group 4, 5 or 6 metal, particularly Zr, Hf or Ti .
• the ⁇ -ligand preferably comprises an ⁇ 4 or ⁇ 5 open chain or an ⁇ 5 - cyclopentadienyl ring, optionally with a ring or chain carbon replaced by a heteroatom (e.g. N, B, S or P) , optionally substituted by pendant or fused ring substituents and optionally linked by bridge (e.g.
• a 1 to 4 atom bridge such as (CH 2 ) 2 , C(CH 3 ) 2 or Si(CH 3 ) 2 ) to a further optionally substituted homo or heterocyclic cyclopentadienyl ring.
• the ring substituents may for example be halo atoms or alkyl groups optionally with carbons replaced by heteroatoms such as O, N and Si, especially Si and O and optionally substituted by mono or polycyclic groups such as phenyl or naphthyl groups .
• Suitable ⁇ -ligands include those of formula II discussed above. Examples of such homo or heterocyclic cyclopentadienyl ligands are well known in the art (see e.g. EP-A-416815, WO96/04290, EP-A-485821, EP-A-485823, US-A-5276208 and US-A-5145819) .
• the metallocene complex used according to the invention may include other ligands; typically these may be halide, hydride, alkyl, aryl , alkoxy, aryloxy, amide, carbamide or other two electron donor groups.
• Any hydrocarbyl ligand here will generally contain up to 20 carbons, preferably up to 10 carbons, e.g. up to 6 carbons.
• Aryl ligands may have from 6 to 20 ring carbon atoms, preferably 6 to 10 ring carbon atoms .
• support or “carrier” are used interchangeably herein to mean any material capable of supporting catalytically active compounds.
• the support material for use in the invention preferably comprises an organic polymer, preferably an organic porous polymer provided in the form of distinct particles.
• the support material will comprise porous polymer particles optionally cross-linked by physical or chemical means, for example using conventional cross- linking agents, e.g. divinylbenzene .
• Preferred support materials include acrylate polymer particles or styrene- divinylbenzene polymer particles.
• the optionally cross- linked polymer backbone may be considered to form the support .
• the term "functionalised support” is used to define any support which has been functionalised so as to carry heteroatoms on its surface capable of forming a chemical bond with the titanium catalyst precursor.
• suitable functionalised supports are therefore those which carry at least one XH group in which each X is independently an organic group and H is an active hydrogen atom attached to a heteroatom in the organic group X, the heteroatom having at least one electron pair available for coordination to the precursor.
• Suitable heteroatoms which may be present in the organic group X are those of groups 15 and 16 of the Periodic Table, preferably, O, P, S and N, particularly O.
• Preferred functionalised supports for use in the invention are those having a pK a ⁇ 30, preferably ⁇ 25, more preferably ⁇ 20.
• Particularly preferred for use in the invention are organic polymer supports carrying -OH, -N(alkyl)H or -NH 2 groups.
• polymer supports comprising divinylbenzene cross-linked polystyrene particles modified to carry functional hydroxy groups.
• Functional groups available as attachment sites may be introduced by conventional techniques, for example using a functionalised monomer when preparing the co-polymer.
• functional groups may be introduced by appropriate modification (e.g. chemical modification) of a non- functionalised co-polymer.
• Functionalised supports for use in the invention may, for example, be prepared in a manner analogous to that described by Ellingsen et al . , J. Chrom. 535:147. 1990.
• a polymeric support as opposed to a conventional silica support is also believed to give rise to polymers suitable for use in electrical insulation applications.
• the use of silica particles in a polymerisation catalyst may give rise to "cracks" in the eventual polymer through which moisture or water may be able to seep. Such polymers are therefore unsuitable for protecting electrical cables and cannot act as insulators.
• the functionalised supports of the present invention are believed to give rise to polymers free from such cracks and therefore have wide spread applications in the field of electrical insulation.
• the heteroatoms which bind to the titanium catalyst precursor may be attached to the functionalised support by separate organic groups, or may be bound to two heteroatoms which form part of the same organic group, e.g. the hydroxyl groups present in a diol .
• Suitable organic groups XH include C x . w alcohols, especially C ⁇ . 6 alcohols, C x _ 10 amines, especially C ⁇ _ 6 amines, thiols, especially C 1 . 6 thiols, optionally substituted aryl groups carrying NH, OH or SH moieties, e.g. benzyl alcohol, phenol, aniline all preferably bound to the Support by the 4-position of the benzene ring. Further suitable groups will be readily determined by the skilled artisan.
• the XH group may have two or more heteroatoms and the titanium catalyst precursor may bind to one or both heteroatoms on the same organic group.
• Suitable XH groups in this regard include diamines and diols such as (1,2- dihydroxyethyl) phenyl or ethylene glycol .
• the titanium catalyst precursor has two sites available for binding heteroatoms it is obviously more likely that the titanium catalyst precursor will bond to two heteroatoms on adjacent XH groups if there is a high surface density of XH groups present on the support.
• the titanium catalyst precursor will bind to a single XH group irrespective of whether it carries further possible coordination sites.
• the catalyst precursor binds to a diol present on the support surface
• the resulting polymer may have a broader molecular weight distribution.
• the catalyst precursor binds to a single heteroatom present on the support surface it is envisaged that a polymer with a narrower molecular weight distribution will result.
• the catalysts described above may be used in combination with a cocatalyst or catalyst activator.
• co-catalyst and “activator” are used interchangeably herein to define any compound or component which is capable of activating a titanium catalyst precursor following attachment to the support or capable of activating the polymerisation active metal complex.
• the activator compound should preferably be one capable of stabilising a titanium catalyst without affecting its ability to function as a catalyst and must be sufficiently labile to permit displacement by an olefin monomer or other polymerisable species during polymerisation.
• the supported activator will be non-coordinating or weakly coordinating towards the titanium.
• the catalyst system herein described may be used in the absence of a co-catalyst.
• a cocatalyst may be used.
• Suitable cocatalysts are well known and include alkyl metal compounds, in particular alumoxanes .
• Suitable alumoxanes include C ⁇ Q alkyl alumoxanes, e.g. methyl alumoxane (MAO) and isobutyl alumoxanes (e.g. tetra and hexaisobutyl alumoxane, TIBAO and HIBAO) , especially MAO.
• Alumoxane co-catalysts are described by Hoechst in WO-A-94/28034. These are linear or cyclic oligomers having up to 40, preferably 3 to 20, -[A1(R")0]- repeat units (where R" is hydrogen, C 1 _ 10 alkyl, preferably methyl, or C 6 _ 18 aryl or mixtures thereof) .
• the supported catalyst of the invention may be prepared by combining the functionalised support and the titanium catalyst precursor in a solvent.
• Suitable solvents for use in the methods of the invention include aliphatic and alicyclic hydrocarbons such as isobutane, butane, pentane, hexane, heptane, cyclohexane, cycloheptane etc. and aromatic compounds such as benzene, toluene, xylene etc.
• Reactions are conveniently carried out in an inert, moisture-free, oxygen-free environment due to the sensitivity of the catalyst components to moisture and oxygen.
• the addition of the titanium catalyst precursor to the support takes place at low temperature e.g. between -90 to 100°C, preferably between -50 and 30°C, preferably at ambient temperature.
• the polymerisation active metal complex is conveniently impregnated into the support after the titanium catalyst precursor has been bound to the support surface.
• the polymerisation active metal complex is added to the dried support complex in toluene optionally in the presence of a cocatalyst, e.g. MAO.
• the final supported catalyst system may be conveniently dried in vacuo or may be used kept in a slurry state for direct use .
• cocatalyst may conveniently be added to the supported titanium catalyst system by standard procedures.
• MAO may be added to the carrier in toluene .
• the supported titanium catalysts herein described may be used to polymerise any olefin or mixture of olefins, for example optionally substituted C 2 - 30 ⁇ - olefins.
• the process of the invention is particularly suitable for the polymerisation of ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3 -methyl-1-butene and 4- methyl-1-pentene, especially preferably ethylene.
• the catalyst systems may be used in any polymerisation or pre-polymerisation process, e.g. gas, slurry or solution phase. Preferably, these will be used in gas or slurry phase reactors.
• Polymerisation according to the invention may be performed using standard polymerisation techniques and using conventional polymerisation reactors, e.g. loop reactors, gas phase reactors, or stirred tank reactors.
• the polymerisation process of the invention is typically conducted in the presence of a diluent.
• a diluent a linear, branched or cyclic saturated hydrocarbon such as butane, propane, pentane, hexane, heptane, octane, cyclohexane or methylcyclohexane, or an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene, or a chlorinated hydrocarbon such as chloroform, methylene chloride, dichloroethane, trichloroethane or tetrachloroethane, or chlorinated aromatic hydrocarbon such as chlorobenzene or dichloro- benzene, may be used.
• aromatic hydrocarbons in particular toluene are preferred.
• the supported catalysts are most usefully employed in either gas or slurry phase processes, both of which are well known in the art.
• the temperature of the polymerisation reaction will typically be in the range of from 0 to 300°C, preferably from 60 to 120°C.
• the pressure employed for the olefin or olefins is typically from 1 to 2000 bars, preferably from 5 to 20 bars.
• the residence time is generally from 1 minute to 20 hours, preferably from 0.5 to 6 hours.
• the reaction temperature will generally be in the range 60 to 110°C (e.g. 85-110°C)
• the reactor pressure will generally be in the range 5 to 80 bar (e.g. 25-65 bar)
• the residence time will generally be in the range 0.3 to 5 hours (e.g. 0.5 to 2 hours) .
• the diluent used will generally be an aliphatic hydrocarbon having a boiling point in the range -70 to +100°C, especially isobutane.
• the reaction temperature used will generally be in the range 60 to 115°C (e.g. 70 to 110°C)
• the reactor pressure will generally be in the range 10 to 25 bar
• the residence time will generally be 1 to 8 hours.
• the gas used will commonly be a non-reactive gas such as nitrogen together with monomer (e.g. ethylene or propylene and/or other comonomers) .
• the polymers produced in accordance with the invention may be formulated together with conventional additives, e.g. antioxidants, UV-stabilizers, colors, fillers, plasticizers, etc. and can be used for fibre or film extrusion or for raffia, or for pipes, or for cable or wire applications or for moulding, e.g. injection moulding, blow moulding, rotational moulding, etc., using conventional moulding and extrusion equipment.
• conventional additives e.g. antioxidants, UV-stabilizers, colors, fillers, plasticizers, etc.
• Figure 1 depicts the MWD curves from GPC analyses for polymer produced with Catalyst III (Example 3) with and without hydrogen.
• Support A is a p- (1, 2-dihydroxyethyl) styrene- co-styrene-co-divinylbenzene polymer prepared by copolymerising p- (1, 2-dihydroxyethyl) styrene, styrene and divinylbenzene .
• the particles formed has a degree of crossbinding of 71%, a porosity of 70% and an average particle diameter of 30 microns. The amount of hydroxy groups measured was 0.80 mmol OH/g.
• Support B is a p- (1, 2-dihydroxyethyl) styrene- co-styrene-co-divinylbenzene polymer prepared by copolymerising p- (1, 2-dihydroxyethyl) styrene, styrene and divinylbenzene in a similar manner as for Support A. The amount of hydroxy groups measured was 0.88 mmol OH/g .
• melt index (MI) and high load melt index were measured using standard conditions; i.e. MI at 190°C, 0.0825in orifice, 2.16kg load; HLMI at 190°C, 0.0825in orifice, 21.6kg load.
• Catalyst I 0.600 g Catalyst I was added to a Schlenck tube containing a magnetic stirrer under argon atmosphere.
• 12 mg (nBuCp) 2 ZrCl 2 was dissolved in 4.0 ml toluene.
• 10 ml toluene and 6.55 ml MAO/toluene (13.1 wt% Al) was mixed.
• 2.61 ml of the solution containing (nBuCp) 2 ZrCl 2 was added. After about 15 minutes reaction 0.72 ml of this solution was added drop-wise by Syringe to the sample of Catalyst I while stirring. Finally the powder was dried for a short time under vacuum yielding 1.00 g catalyst.
• Table 2 Polymerisation conditions and activity data from polymerisations with the heterogeneous catalysts of Examples 2 and 3. Polymerisations in a 1-litre autoclave with 0.5-L isobutane as diluent at 38 bar total pressure, 90°C.
• Table 3 Characteristics of polymer produced with heterogeneous catalysts of Examples 2 and 3. Polymerisations in a 1-litre autoclave with 0.5-L isobutane as diluent at 38 bar total pressure, 90°C.
• a catalyst which comprises a di-alkoxy titanium fragment can be prepared by reaction of TiCl 4 with Support B which contains 4- (1, 2-dihydroxy-ethyl) phenyl groups, i.e. diol groups .
• Support B containing 0.22 mmol diol fragments was suspended in 25 ml pentane and cooled to -78°C.
• a pentane solution containing 0.22 mmol TiCl 4 (taken from a solution made from 242 ⁇ l TiCl 4 in 10 ml pentane) was then added with a syringe while stirring. After two hours the suspension was slowly heated to ambient temperature over a period of 2 hours. The suspension was filtrated, and the solid was dried under reduced pressure, yielding 0.48 g of a yellow-brownish powder. Stored in the glove box.
• Catalyst IV was added 10 ml of a MAO/toluene solution containing 7.4 wt% Al at ambient temperature while stirring. The solution turned immediately brownish. After 15 minutes reaction time the suspension was filtrated, and the solid rest was washed twice with 15 ml portions of pentane. The filtrate was olive- brown, while the solid rest was grey-brown. Drying under reduced pressure yielded 0.56 g powder. Stored in the glove box.
• Catalyst VI was prepared in the same manner as Catalyst IV although employing a more dilute MAO solution.
• Catalyst VI 350 mg Catalyst VI was suspended in 10 ml toluene. Then 6.4 ml MAO/toluene (7.4 wt% Al) was added while stirring. The suspension turned olive. After 0.5 hours reaction time the suspension was filtrated yielding an olive filtrate as observed for Catalyst V. The solid was washed twice with 15 ml portions of pentane, then dried under reduced pressure. Yield: 0.58 g grey-brown powder. Stored in the glove box.
• Catalyst VI containing 0.13 mmol Ti was suspended in 15 ml toluene. Then 21 ⁇ l (0.14 mmol) ethylbenzoate was added with a syringe while stirring. After one hour reaction time, 6.4 ml MAO/toluene (7.4 wt% Al) was added in a similar manner as described for Catalyst V.
• Table 4 Results from polymerisations with heterogeneous catalysts based on TiCl 4 /Support B Polymerisations in a 1-litre autoclave with 0.5-1 isobutane as diluent at 38 bar total pressure, 80°C.

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